Beta-substituted sulfenate esters



U d eelerei q 12,929,824} BETA-SUBSTITUTED SULFENATE ESTE Norman Kharasch, CulyerCity, and RobertB. Langford, Los Angeles, Calif assignors, by direct and mesne 1 5 hols. An excess of the catalyst can be used without disigi lgg m g gg fi fi chemlcalplmpany "advantage, but precautions should be taken to ayoid the No Drawing. Application necernher'ls, 1956 9;? 4.22 4 9 W h release heat 0 Serial No. 627,991 A r 1 R llzme di P' Claims (Cl I The-followlngexamples illustrate the practlce of our I r r 1/1 10 in erltionflfor the case where thesulfenyl derivative is 2,4- This invention relates to the'ma'riufacture bfsulfenate dirlit'r'obeiizerlesulfenyl chloride. a esters and particularly to theman'ufacture of beta-substi x niP G t-* p t' f t i n f ,2 tuted sulfenate esters. 3 epoicz'des with 2, 'izitrobeniehesulfenyl chloride in the We: have found that beta-substituted sulfe'riate-estcrs, PfiYe'fiC f Py Ifit0a'$ma1l,flH-$k, there w Placed can be produced by interactionof a 'IQ'Z epoJgidE-WitHa 0.50 gI"(0.002finole=) of2, l-dinitrobenzenesulfenyl chlosul'fenyl derivative, according togeneral Equation "1, ride -and '5 ml. fi ly ae y c O t e c R1 /Ba erne s," epoiride's o.ozs*rnole ofTablegI was added, followed Y w" A Am 1 3 by3 or 4drops'of py'ridine. The flask was stopperedand "RSX+ f' let stand overnight, at room temperature, in thedark. f 0 r l p Completion (if the reaction was indicated by a negative Where X IS a sulfenyl chlollde, a ny bl'omlder starch-iodide test for the sulfenyl chloride. The yellow sulfenyl thlocyanate or other s y derivative, such or red solutionwas diluted with methylene chloride and a P y acetate, 3 a-slllfefllc anhypoilred onto asilica column. Washingfthe column with dude RSOSR? and the olefin OXIde one of large methylenechloride removed a yellow band, and left a number of Such supstancesz as eifempllfied y ethylene red band (in all cases) on the column. The insoluble oxlde, propylene mode. e lsomerlc butylene p s y: bis(2,4-dinitrophenyl)disulfide was mechanically filtered r6116 OXlde, epichlorohydrln cyclohexefle Oxldeby the column. The yellow eluate was evaporated to drygeneral reaction Shown above Provides a novel and ness and the residue was recrystallized from methylene useful procedure for the synthesis Of a wide variety Of l chloride-petroleum ether 32 36) to give the prod. substituted sulfenate esters. .In accord with the'required uctslisted i Table L F fy, a Suitable aromatic aliphatic y The structures of the products of Table I are arrived denvativ? is reacted Wlth an 1 11101211 quantltyi'of a at by analysis, by consideration of the most probable r p r i mechanism of the reaction [Peters and Kharasch, J. Org. W have fmmdthat t usepf aI1 appropnatecatalysv Chem., 21, 590 (1956)], and especially by alternate lsrhlghly advantageous 1n drivlpg Reactwn 1 o p synthesis of selected examples, via the reactions of the limi- For example, by employing 'y amine, Such T appropriate chlorohydrins and the sulfenyl chloride. as pyridine, thereaction rate is promoted, theacidic Thus as shown in Table L-the identical product was ob. hydrolysis of the P ester that might Otherwise tained either from ethylene oxide and 2,4-dinitrobenzene- Occur 1'8 Prevented y e presenceof the arnine. Only sulfenyl chloride, or from reaction of 2-chloroethanol trace of the Catalyst is TeqlllTed;aI1d, practlcal P (ethylene chlorohydrin) and 2,4-dinitrobenzenesulfenyl P l0 mole of the t y for each 111016 of chloride. Similarly, either propylene oxide or 1-chloro-2- the sulfenyl chloride and epoxide is generally sufiicient propanol gave the same product, in the reaction with 2,4- to P t reaction to go to completion, in reasonable dinitrobenzenesulfenyl chloride. The general procedure time, at room temperature or with only gentle heating. used to prepare the products of Table I can also be ap- In place of pyridine, other amines such as triethylamine plied to other sulfenyl derivatives. Thus, it may be used or Z-methyl-S-ethylpyridine, are also suitable catalysts for with 2 -nitro-4-chlorobenzenesulfenyl chloride, 2-nitro-. Reaction 1. The utility of these is somewhat surprising benzenesulfenyl chloride, 2,4-dinitrobenzenesulfenyl broin view of the report of Moore and Johnson [J. Am. mide, 2,4-dinitrobenzenesulfenyl thiocyanate, 2,4-dinitro Chem. Soc., 57, 1517 (1935)] that sulfenyl halides react benzenesulfenyl. acetate, and, as shown below, in detail, with dry pyridine to form disulfides; but it seems likely with trichlorometlianesulfenyl chloride (Cl CSCl).

TABLE I tlnit tliecatalytiaeilect occurs through formation of a:

such as has been discussed 2,929,824 [resented Marszz, 1960 pyridine-sulfenyl "corrl'plex, byGdodr'nan antl Kharas'ch [J. Am. Chec. Soc., 77, 6541 (1955)] in thereactions of sulfenyl halides with alco- Synthesis of B-chloroalkyl 2,4-tiinitr0llenaetzesulfenates' from 2,4-dinirrobenzenesulfenyl"chloride (IQ and 1,2-

- epoxides ,Qi chlorohydrins v I Analyses Unrei Product (A1=2,4-dinitro- Yield, acted l in Epoxlde or Chlorohydrln phenyl) Percent M.P., absence of Calc'd Found i C. pyridine,

Percent C H N O H N Ethylene oxide ClOHzCHzOSAr 50 120-121 85 34. 53 2. 53 10. 07 34. 45 2. 55 9. 81 2-Ghlor0ethauol. 121-122 34. 53 2. 53 10.07 34. 83 2.76 10.07 Cyclohexene oxide CsHwClO-SAZ' 78 b 140145 95 43. 30 3.90 8.40 43.43 4.16 8. 53 trans-2 Chlorocyclohexauo 80 140445 43. 30 3. 90 8. 40 43. 02 4. 13 8. 28 Propylene oxide OHa(ClCH2)CHOSAr 30 106 107 95 36. 86 3.07 9. 55 36. 91 3. 24 9. 79 1-Ohl0m-2-DropanoL. 55 106-107 36.86 3.07 9.55 36. 55 3.14 9.25 Styrene oxide Yellow oil l 47. 32 3. 10 7.90 47. 80 3.37 7.55

2-Chloro-2-pheny1ethanol. Yellow 011 45 2 C loro-1 phenylethanol..- C5H5CH(OSA1')CH2CI 30 121-122 47 32 3. l0 7. 47. 33 3.20 7. 74 Stilbene oxides (cis and tran No reactlon. l A l I The yields are based on the amounts of 2.4-dlnltrobentone-sulfenyl used.

b The products melt, with decomposition and darkening, in the temperature range-indicated.

0 From the unsy The analytical From the trans o mmctrlcal oxides. the crude products sa Some of the low yields in Table I are undoubtedly caused by traces of moisture present in the reactants and by the fact that the reactions were conducted on a small scale, which makes recovery of product in full amount 'cessful catalyst, but the commercially available and lessexpensive 2-methyl-5-ethylpyridine or triethylamine were also successfully. employed. In the absence of catalyst, certain of these reactions scarcely proceeded at all, but

somewhat more difiicult. That hydrolysis is also involved, 5 catalytic amounts (1 to 5%, by molar proportion to the however, was shown by the occurrence of the well-known sulfenyl chloride) of the tertiary amine served to drive and highly insoluble bis(2-4-dinitrophenyl) disulfidethe reaction to completion in reasonable lengths of time probably by the mechanism described by Kharasch, King, and at low temperatures. The following illustrate the and Bruice, J. Am. Chem. Soc., 77, 931 (1955 Unsynthesis of a' series of beta-chloroalkyl trichloromethanedoubtedly, further precautions in the drying of reagents sulfenates, by reactions of trichloromethanesulfenyl and scaling up of the runs would improve the yields. chloride and selected olefin oxides.

The reaction of 1,2-epoxides is easily illustrated by use One and one-tenth mole (103 g.) of epichlorohydrin of 2,4-dinitrobenzenesulfenyl chloride as the sulfenyl and one mole (186 g.) of trichloromethanesulfenyl chlohalide because the excellently crystalline products from ride were mixed, using 100 m1. of ethylene chloride as the this sulfenyl chloride lend themselves to easy isolation reaction diluent. No apparent reaction was observed on and characterization. It is also for this reason that the remixing these components. Dry pyridine (3 ml.) was action of 1,2-epoxides with 2,4-dinitrobenzenesulfenyl added and the reaction mixture was heated gently (ca. chloride may be recommended for the identification of 50 C.) for two hours, then permitted to stand overcertain olefin oxides, through the characteristic melting night. The following day, completion, of reaction was points of the products [cf., also, Kharasch, J. Chem. Ed., ascertained by a negative test for trichloromethanesul- 33, 585, 1956]. In some cases, however, with unsymfenyl chloride (starch iodide test) and the absence of the metrical 1,2-epoxides, mixture of products may result, typical odor of this sulfenyl chloride. The reaction mixand these latter mixtures may be oils, rather than crystal ture was washed with several portions of cold water, to line solids. This wa observed, for example, in the reremove pyridine hydrochloride, dried, and vacuum disaction of 2,4-dinitrobenzenesulfenyl chloride with styrene tilled. The desired product was a colorless liquid, of oxide. In this instance, the product was a yellow oil, pungent odor, which was obtained in 76% yield of theory which gave the correct elementary analysis for the deand which boiled at 75-76 at 0.2 pressure. The sired reaction product, but which undoubtedly contained index of refraction (n was 1.5321.

a mixture of both possible products shown below Analysis.Calcd. for C H CI OS: C, 17.2; H, 1.79;

(ar=2,4-dinitrophenyl). S, 11.5; CI, 63.7. Found: C, 17.0; H,1.50; S, 11.6;

H Cl, 63.7.

1 The structure of the product was confirmed by alternate synthesis of the identical material from 1,3-dichloro- 0i 2-propanol and trichloromethanesulfenyl chloride. The

and infrared spectra of the products from either route were H identical, as were also the boiling points and visual charl acteristics. The tendency of the product to explode dur- CBHP "CHIC! ing combustion analysis was noted, but a satisfactory 0 analysis was obtained by slow burning of the sample ab- 4 sorbed on barium sulfate.

Ex derlvatlves of Example 3.--Procedures similar to that of Example 2 tliifhlfromethanesulfenyl h an f were used to prepare several other trichloromethanesulc onde have i pamcularly valuable utihtles m a fenate esters. The olefin oxides which were successfully number of apphcatlons' It W therefore consider. h employed in these reactions with trichloromethanesulbeta-chloroalkyl esters of trichloromethanesulfen c acid, fenyl chloride were ethylene oxide, propylene oxide, Such as could be obiamed reactions of m tene-l-oxide, butene-Z-oxide, isobutylene oxide, and stymethanetulfenyl chloride and lz'epoxldes (acFmfjmg to rene oxide. The structures of the products are shown in the reaction of Equation 1), would be of special in Table II. The correctness of the assigned structures Was and t is these which are cited as examples to illustrate confirmed by elemental-y analyses, i f red analyses, and our f The cholce of mdiloromethanewlfgiyl alternate synthesis. For example, in the ease of the prodchloride was also made because of its ready ava lability uct from ethylene oxide the Same substance and the special interest which attaches to reactions of substances which can decompose by free-radical paths C13CS OCI I2CHZCIT to yield trichloromethyl free radicals, a behavior especiala Obtamed y reaction wlth ethylene chlorohydrin; 1y to be anticipated in the reactions of compounds of 5 5 and the Productfrom P py oxide was almost n y Stmture.C.l3CS OR "Y have flilfpemxldlc Ci3CSO-g CHgC1 (rather than the isomer, oii cut-04001.1 characteristics. Accordingly, suitable conditions were CH; Ctr; sought, and found, for carrying out the reaction of trisince the product from propylene oxide and trichlorochloromethanesulfenyl chloride (Cl CSCl) with a series methanesulfenyl was the same as that obtained by reacof 1,2-epoxides. Again, pyridine was found to be a suction of the sulfenyl chloride and 1-ch1oro-2-propanol.

TABLE II Examples of beta-chloroalkyl-trichloromethanesulfenate esters Epoxido Product Yield, 13.13., C./n1u n,"

Percent Ethylene 0xlde. cicriiofiioscoii s5 45.0-4s.0/0.15.. 1.523s Propylene Oxide... C a(CICHi)CHO9OCIa 81 49.550.510.15.. 1.5122 Epichlorohydrin... (ClOHzhCHOSCClak 7e 75.076.0,'0.2...- 1.5321 Butene Oxides 0105 50 0013 85 51.052.0/0.15.. 1.5095 Styrene Oxide CUI'I5CH(CHZCDOSC 74 119 -121.o/0.12 1.5720

b Anaheim-Cale; Clv 63.72%.

w Analysis-Cale;

4 Mixed isomers.

7- o 2; 3.1.79; 8, 11.5; 01, 63.7. Found: 6,1102; H,1.50; S,11.65;

greases Allof the 'new thioperoxides obtained from theiolefin oxides and trichloromethanesulfenyl chloride were dense liquids, colorless wheni pure '(but tending to become yellow when exposed to" light) and having indicesof 're' fraction (h of about l.5.' s

The utility of a catalyst is clearly ration of the products of TableII.

Example 4.A specific example of the syntheses of Example 3' is illustrated by the case of' reaction of ethylene oxide and trichloromethanesulfenyl chloride.

One mole (186 g.) of trichloromethanesulfenyl chloride'was-dissolved in 100ml. of dry ethylene chloride. The mixture was cooled to -5, and to itwas added slowly 1.1 mole (48.4 g.) of ethyleneoxide, dissolved in 50 ml. of ethylene chloride. The reaction flask was fitted with a cold-finger condenser. and the mixture was stirred, while adding 3 ml. of pyridine. The clear solution was leftfor about 15 hours, at room temperature, at which time the test for the sulfenyl chloride-was negative. The mixturewas then washed'with water, to remove the pyridine, dried with anhydrous sodium sulfate, the solvent and excess olefin oxide were-distilled at 0.15 mm. pressure (B.P. 45-56"); yield, 85%. The product was identical with the one obtained by reaction of trichloromethanesulfenyl chloride and 2-chloroethanol.

Analysis.-Calcd. for C I-I' CI OS: C, 15.65; H, 1.74; Cl, 61.03; S, 13.9. Found: C,16.53; H, 1.59; Cl, 60.57; S, 13.05. t 5

This product exploded several times during attempts to carry out the combustion analyses. In the carbon-hydrogen determinations, it was found necessary to dilute thesamples with bariumtsulfate. Repeated analyses did not improve the carbon value found inthe product.

Example 5.-The reaction of Example 4 was carried out precisely as described above, except that the addition shown in the prepaof pyridine was omitted. The test for unreacted sulfenyl chloride (cf. Kharasch and Wald, Anal .-Che m., 27, 996 (1955)) remained strongly positive. After keeping the reaction mixture for twelve days in a sealed flask, at room temperature, the mixture was fractionally distilled. There was recovered 178 g. (0.95 mole) of trichloromethanesulfenyl chloride. Further evidence that essentially no reaction had occurred after. the twelve day period lies in the fact that the distillate gave no evidence of any component boiling in the range to'be expected forthe 2-chloroethyl trichloromethylsulfenate (cf. Example 3).

USES .OF THE PRODUCTS The utilities of the beta-chloroalkyltrichloromethanesulfenate esters as agricultural chemicals was investigated.

(a) As fungicides-TZ-chloroethyl trichloromethane sulfenate (the product from ethylene oxide) eflectively killed S. fructicola at 5 p.p.m. and A. niger and stemphylium sp. at 50 p.p.m. in the agar test plates, showing that the product is an effective fungicide.

The other esters listed in Table 'II also showed positive' fungicidal actions. T

(b) In the control of rust and miIdeWF-I-phenyl-Z- chloroethyl trichloromethanesulfenate showed value in the control of rust and mildew, being 100% effective against rust at 1000 p.p.m. l-phenyl-Z-chloroethyl pchlorobenzenesulfenate was also found to be effective in the control of mildew.

(c) In control of the confused flour beetle.-l-phenyl- 2-chloroethyl trichloromethanesulfenate was also 100% effective in the control of Tribolium confusum, at a dilution of 0.06%, under test conditions.

(d) Other uses.Besides their value as agricultural chemicals, the beta-substituted sulfenate esters (obtainable via Reaction 1) are of value for various other practical purposes. For example: I

(1) The thioperoxides derived by reaction of epoxidized fish, vegetable, or animal oils are useful in small concentrations as additives in the finishing of papers to prevent attack by micro-prganisn tsgnd in paint formulasociation of the thioperoxides derived from trichlorotions, especially in the preparation of coatings for marine 2,4-dinitrobenzenesulfenyl chloride or 2-nitro-4-chlorobenzenesulfenyl'chloride are of value as modifiers and inhibitors of vinyl polymerizations. Because of the wide range of such thioperoxides available, and their abilities to act as free-radical traps, as well as their individual tendencies to undergo scission into free radicals they may be used to generate such radicals in polymer formulations, providing means to inhibit and to modify the. growth of the polymer chain from a vinyl type a aniline ATS-NHCQH: o o Arsocm moi-omooon ll (0) ll ArS-OCH rArfiOCHs 0 (4) As lubricating oil additives: The free-radical dismethanesulfenyl chloride and other sulfenyl derivatives provides a type of behavior which by choice of the appropriate sulfenate, makes these useful as additives to lubricating oils. V i

(5) For improvement of ignition behaviors of diesel fuels: The free-radical dissociation of thioperoxides derived from trichloromethanesulfenyl chloride makes the beta-substituted thioperoxides of this type useful as substances to modify and improve the ignition behaviors of diesel fuels (6) As rubber chemicals: Our methods for the practical synthesis of a large variety of beta-substituted thioperoxides also provides a new group of substances which are of utility in the vulcanization of rubber and the manufacture of rubber products.

DIEPOXIDES Thus far, we have considered only the cases where the sulfenyl derivative is as specified for Equation 1 and the epoxide is a mono-epoxide or a substituted monoepoxide, asfor example-epiphlorohydrin. By using the technique of Example 1, we have also found that-the reaction of a sulfenyl derivative and a diepoxide can be suitably controlled to yield distinct products, as illustrated in the following example, employing 2,4-dinitro-benzenesulfenyl chloride, butadiene diepoxide and pyridine as catalyst.

Example 6.-Into a 125 ml. glass-stoppered Erlenmeyer flask there was placed 3.52 g. (0.015 mole) of 2,4-dinitrobenzene-sulfenyl chloride (M.P. 95-97) and 35 m1. of pure ethylene chloride was added. Butadiene diepoxide (caution: reported to be strongly carcinogenic), 1.29 g. (0.015 mole), was added and ten drops of pure dry pyridine were then added to the reaction mixture. The flask was stoppered and let stand 20 hours at room temperature, in the dark. It was noted, however, that immediately after adding the pyridine, a highly insoluble. material formed. After 20 hours, the yellow solid was collected and washed with dry methylene chloride. By its characteristic appearance and decomposition temperature (290-300) it was judged to be bis(2,4-dinitrophenyl) disulfide (0.8 g.). The yellow filtrate was chromatographed, using g. of silica gel and methylene chloride as eluent. to two excellently crystalline products, one melting at 167-168 (dec.) and obtained (2) The beta-substituted thioperoxides obtained from Final working up of the eluates led' only in 4.2% yield; anti" ene chloride and then from 95% ethanol.

the other melting at 130-131 (dec.), in 27.7% yield,

- based on the sulfenyl chloride used. Although the struc- Analysis.-Higher melting products; presumably of structure A: Calcd. for C H O N S Cl C, 34.59; H, 2.16; N, 10.09. Found: C, 34.32; H, 2.02; N, 10.45. Found (independent analysis on different sample): C, 34.99; H, 2.24. The product was highly explosive under combustion conditions.

AnaIysis.-Lower melting isomer, probably of structure B: Calcd. C H O N SCI: C, 37.44; H, 2.81; N, 8.74; S, 9.98. Found: C, 37.24; H, 2.68; N, 8.91; S, 10.08.

Example 7.The use of 4-chloro-2-nitrobenzenesulfenyl chloride as the sulfenyl chloride in the reaction with an epoxide is illustrated by the following: In a 50 ml., dry flask was placed 2.24 g. (0.01 mole) of 2-nitro-4- chlorobenzenesulfenyl chloride, 25 ml. of dry ethylene chloride, 0.125 mole of ethylene oxide, and 0.3 ml. of

dry pyridine. The flask was stoppered and let stand, at room temperature in the dark, for one day. Completion of the reaction was indicated by a negative starch-iodide test for the sulfenyl chloride. The solvent was removed in vacuo and the residue recrystallized once from methyl- After drying in the vacuum dessicator, the product melted at 99- 100 C.

Analysis.-Calcd. Found: Cl, 26.72.

We claim:

1. Chemical compounds of the general formula NO (X)C H SOCH(R")CHCl wherein X is selected from the class consisting of N Cl and H, and R" is selected from the class consisting of H, lower alkyl and phenyl.

2. Chemical compounds of the general formula for c,H,No,sc1,= 01, 26.44.

NO$(X) CtHzSO CHCH where X is selected from'the class consisting of N0 Cl and H.

3. A mixture of compounds prepared by reacting butadiene diepoxidewith 2,4-dinitrobenzenesulfenyl chloride in equimolar proportions in the presence of pyridine.

4. Z-chloroethyl 2,4-dinitrobenzenesulfenate.

5. Z-chloroethyl 2-nitro-4-chlorobenzenesulfenate.

6. 2-chlorocyclohexyl 2,4-dinitrobenzenesulfenate.

7. l-chloro-Z-propyl 2,4dinitrobenzenesulfenate.

8. 2-chloro-2-phenylethyl 2,4-dinitrobenzenesulfenate.

9. A process for preparing a beta-substituted sulfenate ester comprising contacting a first reactant of the formula RSX Where R is selected from the group consisting of trichloromethyl, nitro-substituted phenyl and nitroand chloro-substituted phenyl and X is selected from the group consisting of chlorine, bromine, thiocyanate and OCOCH with a second reactant selected from the group consisting of (a) compounds of the formula CE2-CHR' where R is selected from the group consisting of H, lower alkyl and phenyl, (b) the epichlorohydrins corresponding to said class (a) compounds, (c) lower cycloaliph'atic epoxrdes, (d) the epichlorohydrins of lower 'cycloaliphatic epoxldes and (e) butadiene diepoxide.

-10. The process of claim 9 wherein the first reactant is 2,4-dinitrobenzene-sulfenyl chloride, the second reactant is butadiene diepoxide and the second reactant is present relative to the first reactant in a 1:1 molar ratio.

11. A process for preparing a beta-substituted sulfenate ester comprising contacting in the presence of a tertiary amine catalyst selected from the group consisting of triethylamine, pyridine and lower alkyl-substituted pyridines a first reactant of the formula RSX where R is selected from the group consisting of trichloromethyl, nitro-substituted phenyl and nitroand chloro-substituted phenyl and X is selected from the group consisting of chlorine, bromine, thiocyanate and OCOCH with a second reactant selected from the group consisting of (a) compounds of the formula GHQ-CHE 0 where R is selected from the group consisting of H, lower alkyl and phenyl, (b) the epichlorohydrins corresponding to said class (a) compounds, (0) lower cycloaliphatic epoxides, (d) the epichlorohydrins of lower cycloaliphatic expoxides and (e) butadiene diepoxide.

12. A process for preparing a beta-substituted sulfenate ester comprising contacting in the presence of a 2- methyl-S-ethyl pyridine catalyst a first reactant of the formula RSX where R is selected from the group consisting of trichloromethyl, nitro-substituted phenyl and nitroand chloro-substituted phenyl and X is selected from the group consisting of chlorine, bromine, thiocyanate and OCOCH with a second reactant selected from the group consisting of (a) compounds of the formula CHr-CHR' 0 where R is selected from the group consisting of H, lower alkyl and phenyl, (b) the epichlorohydrins corresponding to said class (a) compounds, (c) lower cycloaliphatic epoxides, (d) the epi.hlorohydrins of lower cycloaliphatic epoxides and (e) butadiene diepoxide.

13. A process for preparing a beta-substituted sulfenate ester comprising contacting in the presence of a tertiary amine catalyst selected from the group consisting of triethylamine, pyridine and lower alkyl-substituted pyridines, a first reactant of the formula where X is selected from the group consisting of chlorine, bromine, thiocyanate and OCOCH with a second reactant selected from the group consisting of (a) compounds of the formula CH:CHR

where R is selected from the group consistingof H, lower alkyl and phenyl, (b) the epichlorohydrins corresponding to said class (a) compounds, (c) lower cycloaliphatic epoxides, (d) the epichlorohydrins of lower cycloaliphatic epoxides and (e) butadiene diepoxide.

14. A process for preparing a beta-substituted sulfenate ester comprising contacting in the presence of a tertiary amine catalyst selected from the group consisting of triethylamine, pyridine and lower alkyl-substituted pyridines,

i a first reactant of the formula RSX where R is selected from the group consisting of trichloromethyl, nitro-substituted phenyl and nitroand chloro-substituted phenyl and X is selected from the group consisting of chlorine, bromine, thiocyanate and OCOCH with ethylene oxide.

15. A process for preparing a beta-substituted sulfenate ester comprising contacting in the presence of a tertiary amine catalyst selected from the group consisting of triethylamin'e, pyridine and lower alkyl-substituted pyridines,

.a first reactant of the formula RSX where R is selected from the group consisting of trichloromethyl, nitro-substituted phenyl and nitroand chloro-suhstitnted phenyl and X is selected from the group consisting of chlorine, bromine, thiocyanate and OCOCH with styrene oxide.

16. A process for preparing a beta-substituted sulfenate ester comprising contacting in the presence of a tertiary amine catalyst selected from the group consisting of tnethylamine, pyridine and lower alkyl-substituted pyridines, a first reactant of the formula RSX where R is selected from the group consisting of trichloromethyl, nitro-substituted phenyl and nitroand chloro-substituted' phenyl and X is selected from the group consisting of chlorine, bromine, thiocyanate and OCOCH with epichlorohydrin.

17. The process for preparing a beta-substituted sulfenate ester comprising contacting in the presence of a pyridine catalyst a first reactant of the formula RSX wherein R is selected from the group consisting of trichloromethyl, nitro-substituted phenyl and nitroand' chloro-substituted phenyl and X is selected from the group consisting of chlorine, bromine, thiocyanate and OCOCH with butadiene diepoxide.

vdine and lower alkyl-substituted pyridines with a second reactant selected from the group consisting of (a) compounds of the formula where R is selected from the group consisting of H, lower alkyl and phenyl, (b) the epichlorhydrins corresponding to said class (a) compounds, (0) lower cycloaliphatic epoxides, (d the epichlorohydrins of lower cycloaliphatic epoxides and (e) butadiene diepoxide.

References'Cited in the file of this patent Kharasch et al.: Chem. Reviews, vol. 39, pages 323-7 (1946). V

Perold et al.: J.A.C.S., vol. 73, pages 2379-80 (1952). 

1. CHEMICAL COMPOUNDS OF THE GENERAL FORMULA NO2(X)C6H3SOCH(R")CHCL WHEREIN X IS SELECTED FROM THE CLASS CONSISTING OF NO2, CL AND H, AND R" IS SELECTED FROM THE CLASS CONSISTING OF H, LOWER ALKYL AND PHENYL.
 3. A MIXTURE OF COMPOUNDS PREPARED BY REACTING BUTADIENE DIEPOXIDE WITH 2,4-DINITROBENZENESULFENYL CHLORIDE IN EQUIMOLAR PROPORTIONS IN THE PRESENCE OF PYRIDINE. 